CN1265432A - Active cathode and its prepn. - Google Patents
Active cathode and its prepn. Download PDFInfo
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- CN1265432A CN1265432A CN00102680A CN00102680A CN1265432A CN 1265432 A CN1265432 A CN 1265432A CN 00102680 A CN00102680 A CN 00102680A CN 00102680 A CN00102680 A CN 00102680A CN 1265432 A CN1265432 A CN 1265432A
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- Prior art keywords
- interlayer
- catalyst layer
- platinum
- conductive substrates
- nickel
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- 239000000758 substrate Substances 0.000 claims abstract description 71
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 69
- 239000011229 interlayer Substances 0.000 claims abstract description 55
- 239000003054 catalyst Substances 0.000 claims abstract description 49
- 239000010410 layer Substances 0.000 claims abstract description 48
- 238000000034 method Methods 0.000 claims abstract description 44
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 41
- -1 lanthanum metals Chemical class 0.000 claims abstract description 29
- 229910052751 metal Inorganic materials 0.000 claims abstract description 28
- 239000002184 metal Substances 0.000 claims abstract description 28
- 229910000480 nickel oxide Inorganic materials 0.000 claims abstract description 22
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000002360 preparation method Methods 0.000 claims abstract description 18
- 229910052709 silver Inorganic materials 0.000 claims abstract description 14
- 239000004332 silver Substances 0.000 claims abstract description 14
- 229910052746 lanthanum Inorganic materials 0.000 claims abstract description 13
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical group [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims abstract description 12
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 71
- 239000011248 coating agent Substances 0.000 claims description 45
- 238000000576 coating method Methods 0.000 claims description 45
- 229910052759 nickel Inorganic materials 0.000 claims description 32
- 239000000203 mixture Substances 0.000 claims description 30
- 150000001875 compounds Chemical class 0.000 claims description 25
- 229910052684 Cerium Inorganic materials 0.000 claims description 15
- 229910052747 lanthanoid Inorganic materials 0.000 claims description 13
- 229910044991 metal oxide Inorganic materials 0.000 claims description 12
- 229910002651 NO3 Inorganic materials 0.000 claims description 8
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 8
- 229910021518 metal oxyhydroxide Inorganic materials 0.000 claims description 7
- 238000001149 thermolysis Methods 0.000 claims description 7
- 150000002602 lanthanoids Chemical class 0.000 claims description 6
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 5
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 3
- 229910001960 metal nitrate Inorganic materials 0.000 claims 2
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 claims 1
- 230000008569 process Effects 0.000 abstract description 4
- 150000004679 hydroxides Chemical class 0.000 abstract 2
- 239000000243 solution Substances 0.000 description 23
- 239000003014 ion exchange membrane Substances 0.000 description 18
- 238000005868 electrolysis reaction Methods 0.000 description 17
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 14
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 13
- 239000000463 material Substances 0.000 description 10
- 239000001257 hydrogen Substances 0.000 description 9
- 229910052739 hydrogen Inorganic materials 0.000 description 9
- 229910052742 iron Inorganic materials 0.000 description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 8
- 235000011121 sodium hydroxide Nutrition 0.000 description 7
- 239000008151 electrolyte solution Substances 0.000 description 6
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 5
- 238000005260 corrosion Methods 0.000 description 5
- 230000007797 corrosion Effects 0.000 description 5
- 230000008021 deposition Effects 0.000 description 5
- 239000012535 impurity Substances 0.000 description 5
- 229910052707 ruthenium Inorganic materials 0.000 description 5
- WDCYWAQPCXBPJA-UHFFFAOYSA-N 1,3-dinitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC([N+]([O-])=O)=C1 WDCYWAQPCXBPJA-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 239000003513 alkali Substances 0.000 description 4
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000010828 elution Methods 0.000 description 4
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 4
- 229910017604 nitric acid Inorganic materials 0.000 description 4
- 230000000630 rising effect Effects 0.000 description 4
- 239000011780 sodium chloride Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 238000005576 amination reaction Methods 0.000 description 3
- 229910001453 nickel ion Inorganic materials 0.000 description 3
- 231100000572 poisoning Toxicity 0.000 description 3
- 230000000607 poisoning effect Effects 0.000 description 3
- 239000010970 precious metal Substances 0.000 description 3
- 125000006239 protecting group Chemical group 0.000 description 3
- 238000007788 roughening Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 230000001147 anti-toxic effect Effects 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000010894 electron beam technology Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 210000004379 membrane Anatomy 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 238000007750 plasma spraying Methods 0.000 description 2
- 238000007747 plating Methods 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 230000003245 working effect Effects 0.000 description 2
- 229910000975 Carbon steel Inorganic materials 0.000 description 1
- 229910052692 Dysprosium Inorganic materials 0.000 description 1
- 229910052691 Erbium Inorganic materials 0.000 description 1
- 229910052693 Europium Inorganic materials 0.000 description 1
- 229910052688 Gadolinium Inorganic materials 0.000 description 1
- 229910052689 Holmium Inorganic materials 0.000 description 1
- 229910052765 Lutetium Inorganic materials 0.000 description 1
- 229910052779 Neodymium Inorganic materials 0.000 description 1
- 229910052777 Praseodymium Inorganic materials 0.000 description 1
- 229910052773 Promethium Inorganic materials 0.000 description 1
- 229910052772 Samarium Inorganic materials 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 229910052771 Terbium Inorganic materials 0.000 description 1
- 229910052775 Thulium Inorganic materials 0.000 description 1
- 229910052769 Ytterbium Inorganic materials 0.000 description 1
- ICOZZQDVRFJGJT-UHFFFAOYSA-N [Pt].OOO Chemical compound [Pt].OOO ICOZZQDVRFJGJT-UHFFFAOYSA-N 0.000 description 1
- NGIISMJJMXRCCT-UHFFFAOYSA-N [Ru].[N+](=O)(O)[O-] Chemical compound [Ru].[N+](=O)(O)[O-] NGIISMJJMXRCCT-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 210000002469 basement membrane Anatomy 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000010962 carbon steel Substances 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 229910000420 cerium oxide Inorganic materials 0.000 description 1
- OZECDDHOAMNMQI-UHFFFAOYSA-H cerium(3+);trisulfate Chemical compound [Ce+3].[Ce+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O OZECDDHOAMNMQI-UHFFFAOYSA-H 0.000 description 1
- 229910000333 cerium(III) sulfate Inorganic materials 0.000 description 1
- 238000003486 chemical etching Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- KBQHZAAAGSGFKK-UHFFFAOYSA-N dysprosium atom Chemical compound [Dy] KBQHZAAAGSGFKK-UHFFFAOYSA-N 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000007772 electroless plating Methods 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- UYAHIZSMUZPPFV-UHFFFAOYSA-N erbium Chemical compound [Er] UYAHIZSMUZPPFV-UHFFFAOYSA-N 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- UIWYJDYFSGRHKR-UHFFFAOYSA-N gadolinium atom Chemical compound [Gd] UIWYJDYFSGRHKR-UHFFFAOYSA-N 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- KJZYNXUDTRRSPN-UHFFFAOYSA-N holmium atom Chemical compound [Ho] KJZYNXUDTRRSPN-UHFFFAOYSA-N 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- OHSVLFRHMCKCQY-UHFFFAOYSA-N lutetium atom Chemical compound [Lu] OHSVLFRHMCKCQY-UHFFFAOYSA-N 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 description 1
- 150000002815 nickel Chemical class 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000011236 particulate material Substances 0.000 description 1
- 150000003057 platinum Chemical class 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- VQMWBBYLQSCNPO-UHFFFAOYSA-N promethium atom Chemical compound [Pm] VQMWBBYLQSCNPO-UHFFFAOYSA-N 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical class O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 238000010301 surface-oxidation reaction Methods 0.000 description 1
- GZCRRIHWUXGPOV-UHFFFAOYSA-N terbium atom Chemical compound [Tb] GZCRRIHWUXGPOV-UHFFFAOYSA-N 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- NAWDYIZEMPQZHO-UHFFFAOYSA-N ytterbium Chemical compound [Yb] NAWDYIZEMPQZHO-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
- C25B11/091—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds
- C25B11/093—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds at least one noble metal or noble metal oxide and at least one non-noble metal oxide
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Electrodes For Compound Or Non-Metal Manufacture (AREA)
- Catalysts (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
Abstract
An activated cathode comprising an electrically conductive substrate, an interlayer comprising a nickel oxide formed on the surface of the electrically conductive substrate, and a catalyst layer containing at least one lanthanum component selected from oxides and hydroxides of lanthanum metals and at least one platinum component selected from platinum metals and silver and oxides and hydroxides thereof formed on the interlayer. A process for the preparation of an activated cathode is also disclosed.
Description
The present invention relates to a kind of activated cathode with well attached performance and long service life and preparation method thereof, this negative electrode is particularly suitable for brinish and stablizes electrolysis.
In electrolytic industry, it is very important reducing energy expenditure.Particularly considerable attention is thrown into and reduced on the bath voltage.
Employing is combined with the saline electrolysis industrialization of adopting ion-exchange membrane as anode by the insoluble petal electrode of metal oxide containing precious metals system, almost can eliminate some principal elements that cause bath voltage to raise fully.On the other hand, adopt soft steel up to now always, cause the high hydrogen overpotential of 300-400mv as negative electrode.Adopt the material that comprises stainless steel, nickel and nickel plating to replace carbon steel recently.Yet in order to reach the purpose of the overvoltage that reduces hydrogen, these surrogates still have some shortcomings.
In order to reduce because of increasing the overvoltage that surface area produces, attempted certain methods, for example comprise that from alloy deposits elution goes out the method for some composition, comprises the method for plasma spraying particulate material and comprise the suspension electric plating method.Yet, be that the surface irregularity of negative electrode may damage ion-exchange membrane, and yet not enough on the effect that reduces bath voltage by the shortcoming of the negative electrode of these methods preparation.
The main recently a kind of method that reduces the negative electrode overvoltage that adopts comprises and adopts platinum or its oxide compound coating nickel substrate as catalyst component.The example of known employing platinum metal oxides coating comprises following method: the solution that a kind of method pin contains platinum metal oxides is coated on the heated metal base, and the coated material of roasting is to make oxide compound (JP-B-55-22556 (speech used herein " JP-B " means " Japanese patent application of having authorized ")) such as ruthenium in its surface then; A kind of method comprises that the powder of electroplating oxide compounds such as rutheniums by suspension is attached to (JP-B-59-48872, JP-B-60-13074) on the nickeliferous substrate surface; A kind of method comprises makes for example composite oxides (JP-A-59-232284 (speech used herein " JP-A " means " the not Japanese patent application of Shen Ding announcement ")) of nickel and ruthenium of metal.By the negative electrode of these method preparations, the overvoltage of hydrogen is low, and the overvoltage of hydrogen is subjected to for example influence of iron of impurity in the electrolytic solution hardly.Yet, because comprising, these methods adopt unsettled oxide compound as negative electrode, made thus negative electrode does not have enough weather resistance, thereby its shortcoming is often to shorten working time.
On the other hand, known a kind of negative electrode, it comprises platinum, particularly platinum or its alloy (JP-A-57-23083) of electroless plating in the substrate of being made by nickel etc.The hydrogen overpotential of this negative electrode is low, and weather resistance is long, but its shortcoming is easily by the iron poisoning for example of the impurity in the electrolytic solution.In other words, the negative electrode of this platinum coating is highstrung to the impurity in the electrolytic solution, particularly iron ion.Therefore, the negative electrode of coating platinum even under the situation that is no more than 1ppm, lose the low effect of its hydrogen overpotential can be at the amount of iron ion for a short time.Yet, because most electrolyzer and pipeline thereof are made by ferruginous material, be extremely difficult so will avoid the existence of iron ion in electrolytic solution, this can cause the deterioration of negative electrode inevitably.
In order to overcome these difficulties, someone proposes a kind of electrolytic negative electrode that is used for, it comprises the catalyst layer that is coated on the negative electrode, this catalyst layer comprises at least a (JP-B-6-33492) at least a and cerium, cerium oxide and the cerium oxyhydroxide in platinum, platinum metal oxides and the platinum oxyhydroxide.In general, cerium chemically is being active, so it almost can not exist in soda lye.Again because the specific conductivity of cerium is low, so it can increase the resistance of aforementioned coating undoubtedly.Therefore, be impracticable with cerium as the cathod catalyst of saline electrolysis.Yet when being mixed and made into compound coating with aforesaid platinum composition, the cerium composition is extremely stable in the alkali of high density, can make the low cathode of hydrogen overpotential, and this coating has fabulous weather resistance, anti-toxic and enough specific conductivity.The chances are for this because the cerium composition in the coating forms the cerous hydroxide that is insoluble in the high concentration alkali, and improve the cause of iron overvoltage of deposition reaction on the platinum composition.
Yet, owing to above-mentioned negative electrode with high reactivity and anti-iron poisoning can only be coated in its substrate with the porous catalyst layer, so the adhesion property between catalyst coat and substrate is also relatively poor.Therefore, the platinum composition that contains and the catalyst coat of cerium composition can peel off or can partly come off from substrate from substrate.When revealing these defectives, can make substrate be exposed in the high aqueous solution of alkali concn and corroded, reduce the work-ing life of electrode significantly.Substrate also can be dissolved in the high aqueous solution of alkali concn in addition, increases the content of impurity in the product.
Therefore the purpose of this invention is to provide a kind of activated cathode, its catalyst coat is not easy to peel off or be not easy fall in flakes, the method that can effectively utilize its distinctive high reactivity and anti-toxic and this activated cathode of preparation is provided.
Can embody above-mentioned purpose of the present invention significantly according to following detailed description and some embodiment.
Above-mentioned purpose of the present invention realizes by preparing a kind of activated cathode, this activated cathode comprises conductive substrates, the interlayer that comprises nickel oxide that forms and the catalyst layer that forms with surface on interlayer on the conductive substrates surface, this catalyst layer comprise at least a lanthanum composition that is selected from lanthanide metal oxide and oxyhydroxide and at least a be selected from platinum metals and silver with and the platinum composition of oxide compound and oxyhydroxide.
Above-mentioned purpose of the present invention also can adopt a kind of method for preparing activated cathode to realize, this method comprises that elder generation forms the interlayer that comprises oxide compound on the substrate surface of conduction, on the surface of interlayer, form catalyst layer then, this catalyst layer comprise at least a lanthanum composition that is selected from lanthanide metal oxide and oxyhydroxide and at least a be selected from platinum metals and silver with and the platinum composition of oxide compound and oxyhydroxide.
Hereinafter the present invention will be described further.
In the present invention, comprise the interlayer of nickel oxide between conductive substrates and catalyst layer.This interlayer can prevent electrolytic solution for example the highly basic of the high density caustic soda that produces of saline electrolysis infiltrates and corrosion substrate and go out impurity from elution wherein.In addition, be that conductive substrates by nickel system surface oxidation takes place in its surface forms if contain the interlayer of nickel oxide, then formed interlayer has maximum adhesion property, because interlayer and substrate are a kind of materials each other originally.Therefore, the incrust or fall in flakes of interlayer that so forms.
From the viewpoint of conductivity and chemical stability, conductive substrates is preferably by stainless steel, titanium, nickel and carbon material manufacturing.Preferred especially the employing is the conductive substrates of nickel system at least from the teeth outwards, because can be with the conductive matrices roasting, whole in its surface formation nickel oxide layer be as interlayer.Even substrate and interlayer can not wholely form, nickel on substrate surface and the nickel in the interlayer also have good avidity mutually, thereby the adhesion property between having improved these two layers.The thickness of conductive substrates and porosity are not subjected to concrete restriction.Yet the thickness of conductive substrates and porosity difference preferred about 0.05 to 5mm and about 10% to 95% in practice.
Thereby under the situation of roasting conductive substrates with its surface of oxidation and generation nickel oxide interlayer, conductive substrates its surface at least must be made by nickel.Only need in air, to add this substrate of thermal bake-out and just can form interlayer.Nickel interreaction in airborne oxygen and the substrate surface layer, the oxide compound Ni of generation nickel
(1-x)O.Though the composition of nickel oxide depends on its formation condition, this nickel oxide is anoxybiotic normally, therefore has the character of P-N-type semiconductorN.Maturing temperature is 350-550 ℃.The preferred 5-60 of roasting time minute.
On the other hand, when separately forming interlayer on the surface in conductive substrates, preferably with the surface roughening of conductive substrates, to improve its adhesion property to interlayer.Can adopt the sand-blast that comprises pulverized powder, the etch method that adopts solubility acid or plasma spraying method as the method that makes surface roughening.In order to remove particulate pollutant for example metal and organism from the surface of substrate, preferably adopt chemical etching method.In this case, the consumption of preferred conductive substrates is 50-500g/m
2
On the uneven surface of conductive substrates, form nickel oxide layer then as interlayer.The method that forms nickel oxide layer for example is included in the coating solution that coating on the surface of matrix comprises nickel ion, the dry coating material, make the coated material thermolysis then, described coating solution is that nickelous nitrate or single nickel salt are dissolved in nitric acid or the sulfuric acid, and water weighing apparatus is released this formulations prepared from solutions again.If combination adopts the liquid that comprises nickelous chloride and hydrochloric acid as coating solution, then substrate can be by excessive corrosion, so that the adhewsive action of substrate surface descends in coating, drying and calcination steps.This just is difficult to obtain to have the interlayer of adequate thickness.In other words, be acid, on substrate surface, form and keep stable nickel oxide importantly making coating solution.And coating solution needs by compound and solvent preparation that can not the excessive corrosion substrate.
When the method that adopts the direct heating substrate or adopt and apply solution earlier and be coated in the substrate, when the interlayer for preparing of the method for the coated material of roasting is too thick then, can cause tangible ohmic loss.Otherwise, when the interlayer of preparation like this is too thin, may be not enough at the bottom of the protecting group.Therefore, preferred interlayer optimum thickness is 0.1-100 μ m.
Then, adopt catalyst layer to cover the surface of the interlayer that so forms.Catalyst layer forms a kind of mixed coating, wherein comprise at least a lanthanide metal oxide and oxyhydroxide (hereinafter being called " lanthanum composition ") and at least a platinum metals and silver with and oxide compound and oxyhydroxide (hereinafter being called " platinum composition ").Platinum composition in the catalyst layer and lanthanum composition are enough to the anti-for example poisoning of the iron ion etc. of soda lye of electrolytic solution of polluting probably, can also make the platinum composition keep it to reduce the effect of hydrogen overpotential simultaneously.The preferred method that forms catalyst layer comprises coating solution is coated on the surface of interlayer, make coating carry out thermolysis then, be dissolved with in nitrate, vitriol, amino title complex and the nitro title complex of lanthanide series metal, platinum metals and/or silver any in the described coating solution.
Lanthanide series metal is that the element of ordination number 57-71 is the general name of lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium and lutetium.In the present invention, most preferably adopt cerium.In more detail, cerium can be dissolved in the form of cerous nitrate or cerous sulfate in the coating solution.In activated cathode of the present invention, cerium exists with the oxide compound of cerium or the form of oxyhydroxide.
The platinum metals comprises platinum, palladium, ruthenium and iridium.Except these platinum metals, also can adopt silver as catalyst metal.These metals can adopt with the form of element, also can adopt with the form of oxide compound or oxyhydroxide.If employing platinum, preferably the form with dinitrobenzene two aminates is dissolved in platinum in the coating solution, if adopt ruthenium, preferably the form with the nitric acid ruthenium is dissolved in ruthenium in the coating solution.
The blending ratio of platinum and lanthanum is calculated by mole percentage ratio, is preferably 40: 60-80: 20.The coating solution that wherein is dissolved with various catalyst metal salts is coated on the surface of the substrate that has formed interlayer in the substrate, and drying, roasting are to form catalyst layer then.Can descend dry 5-20 minute at temperature 40-80 ℃.At temperature 350-550 ℃ of following roasting 5-60 minute.So the catalyst layer that forms may be thick.Yet owing to adopt expensive precious metal, so the optimum thickness of catalyst layer is about 0.1 to 10 μ m, the best overlay capacity of catalyzer is about 0.5 to 5g/m on the cathode area
2
Adopt the occasion of negative electrode of the present invention in the saline electrolysis process, corrosion resistant fluoro-resin basement membrane is best suited for the ion-exchange membrane as separatory membrane.Preferably make this negative electrode and aforesaid ion-exchange membrane take place to contact closely to reduce bath voltage.In this structure, cathode substrate need be a porous, and the gas that electrolysis is produced is overflowed easily.In addition, as the anode of opposite electrode preferably with the undissolved electrode (DSE, DSA) of metal oxide containing precious metals coating.In most of the cases, anode is contacted with ion-exchange membrane.Therefore similar to negative electrode, anode also is preferably porous.Before the beginning electrolysis, can adopt mechanical means that various films are adhered to one another.Another kind of scheme be these films can be in electrolytic process about 0.1 to 30kgf/cm
2Pressure under adhered to one another.The brinish electrolysis for example can be at temperature 60-90 ℃ and current density 10-100A/dm
2Under carry out.
In the present invention, on the surface of substrate, form interlayer.Interlayer can prevent that salts solution from touching and corrode substrate, can prevent that again the metallic nickel in the substrate from polluting catalyst layer with nickel ion simultaneously.In most of the cases, negative electrode of the present invention contacts with ion-exchange membrane in electrolytic process.When the nickel contamination catalyst layer, nickel can be from the cathodic migration to the ion-exchange membrane on, move in some cases on the anode, this may produce adverse influence to ion-exchange membrane or anode.As mentioned above, pollute the inside of catalyst layer, also make ion-exchange membrane and anode be subjected to protecting indirectly by preventing nickel ion.
Further illustrate in greater detail the present invention with reference to the following example, but will be understood that the present invention is not limited to these embodiment.
Embodiment 1
The electrolysis area is 100cm
2(width: 5cm; Highly: being prepared as follows of electrolyzer 20cm):
Adopt nickel screen (aperture: 8mm (great majority) and 6mm (minority); Thickness: 1mm) as cathode substrate, adopt particulate alumina (60 order) thoroughly with the nickel screen roughening, and with the boiling hydrochloric acid etching of 20% (weight).Then in stoving oven in 500 ℃ air atmosphere roasting cathode substrate 20 minutes, its surface is gone up forms the nickel oxide interlayer.
Being cerous nitrate and dinitrobenzene two amination platinum to be dissolved in the nitric acid solvent of 8% (weight) in 1: 1 with mol ratio then, is the coating solution of 5% (weight) with the preparation total concn.The coating solution that adopts brush so to prepare is coated on two surfaces of nickel screen, and is dry down 60 ℃ of temperature, then at electric furnace in 500 ℃ of following roastings 20 minutes.With this program triplicate.Finally making the catalyzer overlay capacity is 4g/m
2Activated cathode.Adopt the electron beam spectrometer analysis to form the section of the Ni-based matter of catalyst layer thereon then.Found that the not nickeliferous composition of catalyst layer, the nickel oxide that this proof constitutes interlayer can prevent that substrate from being come out by elution.
Above-mentioned negative electrode and titanium DSE porous anode are come in contact, to form electrolyzer with Nifion 981 (Du Pont's production) both sides that ion-exchange membrane is opposite.Speed anode chamber with 4ml/min provides saturated brine as anolyte then, provides pure water with the speed of 0.4ml/min to cathode compartment, carries out electrolysis under 90 ℃ of temperature and electric current 50A.As a result, bath voltage is 3.35V.Obtain 33% soda lye from the outlet of cathode compartment, current efficiency is 97%.After electrolysis 10 days (have 1 day in 10 days and stop energising), bath voltage rising 10mV, but current efficiency still remains on 97%.Dismantle electrolyzer then, analyze ion conversion film.Found that on ion-exchange membrane, there is not nickel deposition.
Embodiment 2
Nickelous nitrate being dissolved in the nitric acid solvent of 8% (weight), is the coating solution of 5% (weight) with preparation concentration, and with its be coated in embodiment 1 on the identical cathode substrate used.Then in stoving oven in 500 ℃ air atmosphere the coated material of roasting, form the oxide compound of nickel in its surface.Cerous nitrate and dinitrobenzene two amination platinum (mol ratio is 1: 1) are dissolved in the nitric acid solvent of 8% (weight), are the coating solution of 5% (weight) with the preparation total concn.The coating solution of so preparation is divided on several the two sides that are coated in substrate, dry down 60 ℃ of temperature, then in the electric furnace electricity in 500 ℃ of following roastings of temperature 20 minutes.With this operation triplicate, be 4g/m to make final catalyzer overlay capacity
2Activated cathode.Formed the section of the nickel substrate of catalyst layer then thereon with the electron beam spectrometer analysis.Found that the not nickeliferous composition of catalyst layer, the nickel oxide that this proof constitutes interlayer can prevent that substrate from being come out by elution.
Install with embodiment 1 in the identical electrolyzer that uses, different is the above-mentioned negative electrode of employing.Under condition same as described above, carry out electrolysis then.Bath voltage is 3.30V as a result.Obtain 33% soda lye from the outlet of cathode compartment, current efficiency is 97%.After electrolysis 10 days (have 1 day in 10 days and stop energising), bath voltage rising 10mV, but current efficiency still remains on 97%.Dismantle electrolyzer then, analyze ion-exchange membrane.Found that on exchange membrane, there is not nickel deposition.
The comparative example 1
Adopt with embodiment 1 in identical method prepare electrode, different is not form interlayer.Analyze so section of the electrode of preparation then.Found that the nickel composition in the substrate has polluted catalyst layer.Adopt this electrode to form electrolyzer then.Under the condition identical, carry out electrolysis with embodiment 1.In the electrolytic starting stage, bath voltage reaches 3.30V.Obtain 32% soda lye from the outlet of cathode compartment, current efficiency is 96%.After electrolysis 10 days (have 1 day in 10 days and stop energising), bath voltage rising 50mV, current efficiency drops to 94%.Dismantle electrolyzer then, analyze ion-exchange membrane.Found that some overstrike on the surface of ion-exchange membrane.Thereby find nickel deposition is arranged on ion-exchange membrane.
The comparative example 2
The identical electrode that adopts among preparation and the embodiment 1, different is employing platinichloride replaces cerous nitrate and dinitrobenzene two amination platinum as the original material of catalyzer.So section of the electrode of preparation of observation then.Found that, polluted catalyst layer from the nickel composition in the interlayer.Adopt this electrode to form electrolyzer then.Then under the condition identical, carry out electrolysis with embodiment 1.In the electrolytic starting stage, bath voltage reaches 3.30V, obtains 32% soda lye from the outlet of negative electrode, and current efficiency is 96%.After electrolysis 10 days (have 1 day in 10 days and stop energising), bath voltage rising 50mV, current efficiency drops to 95%.Dismantle electrolyzer then, analyze ion-exchange membrane.Found that some overstrike on the surface of ion-exchange membrane.Therefore finding has nickel deposition on ion-exchange membrane.
Activated cathode according to the present invention comprises the substrate of conduction, at interlayer that comprises nickel oxide that forms on the substrate surface and the catalyst layer that on interlayer, forms, this catalyst layer comprise at least a lanthanide metal oxide and oxyhydroxide and at least a be selected from platinum metals and silver with and the metal of oxide compound and oxyhydroxide.
This negative electrode comprises the interlayer that comprises nickel oxide that forms thereon.Adopt this structure, can be in preparation process at the bottom of the protecting group with the mal-condition of anti-heating and roasting etc.And the contained composition nickel inside that can not pollute catalyst layer for example in the substrate.When above-mentioned structure can and rise in the overvoltage effect of keeping platinum composition and lanthanum composition landing low hydrogen and prevents to be poisoned by iron etc., at the bottom of the protecting group and prevent that catalyst layer from being polluted by external material, therefore prolonged the work-ing life of negative electrode.
In addition, by preparing the substrate that has nickel at least from the teeth outwards, make and all contain nickel in substrate and interlayer, this just can further improve the adhesion property between two layers.The lanthanum preferred cerium that comprises in catalyst layer, cerium can be kept platinum and not poison basically.
The invention still further relates to a kind of method for preparing activated cathode, this method, it is included in and forms the interlayer that comprises nickel oxide on the surface of conductive substrates, on the surface of interlayer, form catalyst layer then, this catalyst layer comprise at least a lanthanide metal oxide and oxyhydroxide and at least a be selected from platinum metals and silver with and the metal of oxide compound and oxyhydroxide.
In the present invention, the interlayer of being made by nickel oxide can be formed the part of substrate by the roasting substrate.Can provide intensity height, long service life, middle layer not to peel off or the negative electrode of fall in flakes not by this structure.
The metal-salt preferably nitrate or vitriol rather than the muriate that in coating solution, comprise.Otherwise substrate may be reduced the intensity of electrode by excessive corrosion.Adopt nitrate or vitriol can avoid this shortcoming.
The preparation catalyst layer preferred method comprise with the coating solution be coated on the surface of interlayer, make this coating thermolysis then, be dissolved with in nitrate, vitriol, ammonia complex and the nitro complex compound of lanthanide series metal, platinum metals and/or silver any in the described coating solution.Adopt this method to prepare and have highly active negative electrode.
Though understand the present invention in detail with reference to specific embodiment of the present invention, to those skilled in the art, obviously can in content of the present invention and scope, do various changes and improvement to the present invention.
Claims (12)
1. activated cathode, it comprises conductive substrates with surface, at interlayer that mainly comprises nickel oxide that forms on the surface of described conductive substrates and the catalyst layer that on described interlayer, forms, this catalyst layer comprise at least a lanthanum composition that is selected from lanthanide metal oxide and oxyhydroxide and at least a be selected from platinum metals and silver with and the platinum composition of oxide compound and oxyhydroxide.
2. the activated cathode of claim 1, the surface of wherein said conductive substrates comprises nickel, and described lanthanum composition comprises at least a in the oxide compound of cerium and the oxyhydroxide.
3. method for preparing activated cathode, this method is included in and forms the interlayer that comprises nickel oxide on the surface of conductive substrates, on the surface of described interlayer, form catalyst layer then, this catalyst layer comprise at least a lanthanum composition that is selected from lanthanide metal oxide and oxyhydroxide and at least a be selected from platinum metals and silver with and the platinum composition of oxide compound and oxyhydroxide.
4. the method for claim 3, this method comprise that preparation has conductive substrates, heating and the roasting conductive substrates of nickel control surface, to form the interlayer that comprises nickel oxide thereon.
5. the method for claim 3, this method comprise and being coated on the described conductive substrates wherein being dissolved with the nitrate of nickel or the coating solution of vitriol, make this coating thermolysis then, to make the interlayer that comprises nickel oxide in substrate.
6. the method for claim 3, this method comprise with the coating solution be coated on the surface of described interlayer, make this coating thermolysis then, on interlayer, to form catalyst layer, be dissolved with at least a compound in nitrate, vitriol, amino title complex and the nitro title complex of lanthanide series metal, platinum metals and/or silver in the described coating solution.
7. the method for claim 3, this method comprise with the coating solution be coated on the surface of described interlayer, make this coating thermolysis then, on interlayer, to form catalyst layer, be dissolved with at least a compound in nitrate, vitriol, amino title complex and the nitro title complex of at least a compound in lanthanide series metal nitrate, vitriol, amino title complex and the nitro title complex and platinum metals and/or silver in the described coating solution.
8. the method for claim 3, this method comprise with the coating solution be coated on the surface of described interlayer, make this coating thermolysis then, on interlayer, to form catalyst layer, be dissolved with at least a compound and platinum metals and/or the nitrate of silver and at least a compound in the vitriol in lanthanide series metal nitrate and the vitriol in the described coating solution.
9. the activated cathode of claim 1, wherein the thickness of conductive substrates is about 0.5 to 5mm, porosity is about 10% to 95%.
10. the activated cathode of claim 1, wherein the thickness of interlayer is 0.1-100 μ m.
11. the activated cathode of claim 1, wherein the thickness of catalyst layer is about 0.1 to 10 μ m.
12. the activated cathode of claim 1, wherein the catalyst layer overlay capacity of cathode surface is about 0.5 to 5g/m
2
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP45810/1999 | 1999-02-24 | ||
| JP04581099A JP4142191B2 (en) | 1999-02-24 | 1999-02-24 | Method for producing activated cathode |
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| Publication Number | Publication Date |
|---|---|
| CN1265432A true CN1265432A (en) | 2000-09-06 |
| CN1167833C CN1167833C (en) | 2004-09-22 |
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| CNB001026801A Expired - Lifetime CN1167833C (en) | 1999-02-24 | 2000-02-24 | Active cathode and its prepn. |
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| Country | Link |
|---|---|
| US (1) | US6312571B1 (en) |
| JP (1) | JP4142191B2 (en) |
| CN (1) | CN1167833C (en) |
| AU (1) | AU755255B2 (en) |
| DE (1) | DE10007448B4 (en) |
| IT (1) | IT1315841B1 (en) |
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-
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- 2000-02-17 AU AU17552/00A patent/AU755255B2/en not_active Expired
- 2000-02-18 DE DE10007448A patent/DE10007448B4/en not_active Expired - Lifetime
- 2000-02-24 IT IT2000RM000089A patent/IT1315841B1/en active
- 2000-02-24 CN CNB001026801A patent/CN1167833C/en not_active Expired - Lifetime
- 2000-02-24 US US09/511,989 patent/US6312571B1/en not_active Expired - Lifetime
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Also Published As
| Publication number | Publication date |
|---|---|
| CN1167833C (en) | 2004-09-22 |
| JP4142191B2 (en) | 2008-08-27 |
| ITRM20000089A1 (en) | 2001-08-24 |
| AU1755200A (en) | 2000-08-31 |
| ITRM20000089A0 (en) | 2000-02-24 |
| JP2000239882A (en) | 2000-09-05 |
| IT1315841B1 (en) | 2003-03-26 |
| US6312571B1 (en) | 2001-11-06 |
| DE10007448B4 (en) | 2007-08-02 |
| DE10007448A1 (en) | 2000-08-31 |
| AU755255B2 (en) | 2002-12-05 |
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